Lubricating composition



Patented Apr. 4, 1950 LUBRICATING COMPOSITION David E. Adelson, Berkeley, Calif., assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. ,Application October 24, 1947, Serial No. 782,044

Claims. 1

This invention relates to new and novel products which have properties of greatly improving and stabilizing lubricants. More particularly, this invention pertains to oleaginous materials, especially lubricants, such as mineral lubricating oils, synthetic lubricants of hydrocarbon and non-hydrocarbon origin, and the like, containing a multi-functional additive having detergent and anti-ringsticking properties, which additive also acts as an inhibitor of oxidation and corrosion.

It is ,well known that various lubricants, whether doped or undoped, tend to oxidize and form corrosive bodies and sludge when used in modern engines and machines operating under ordinary conditions, and especially at high speeds, elevated temperatures, heavy loads and other adverse conditions. Also, as lubricants deteriorate during use, hard carbonaceous materials are formed on engine and machine parts, causing scratching and scuffing of movable metal parts, and sticking of valves and piston rings in engines. In addition, lubricants prepared and sold until now are generally incapable of maintaining a continuous lubricating film between movable metal parts; this results in a gradual or even rapid wearing away of the metal parts. The damage thus caused requires replacement of such parts, or even a complete overhauling of the engines-and machines, resulting in expensive loss I of production and time.

In the case of the highest quality non-corrosive, stable undoped mineral lubricating oils, which are highly refined for specific uses, or synthetic lubricants developed for special uses, it has been found that such oils and lubricants are generally highly susceptible to oxidation and deterioration, becoming progressively more and more corrosive in engines and machines even under ordinary operating conditions.

To improve the lubricating properties of oils and synthetic lubricants, it has become the practice to blend therewith one or more additives which have the effect or property of inhibiting deterioration of lubricants and impart to them certain beneficial properties. Thus additives have been specifically designed which have the property of inhibiting corrosion of alloyed bearings such as copper-lead, cadmium-silver and the like, developed for automotive, Diesel and aircraft engines. Acidic oxidation or decomposition components formedin lubricants during use can readily attack these bearings, but are inhibited or prevented from doing this by the formation of a corrosion protective film formed with the aid of the additive on the bearing surface. Additives have also been developed which possess the property of modifying the carbonaceous materials formed by deterioration of lubricants on piston rods, rings and valves and other metal parts in internal combustion engines, automotive and truck engines, aviation engines, high speed Diesel engines, and the like. These additives serve a very important function because by modifying this carbonaceous material so that it can be removed easily, the tendency of engine parts to become stuck is inhibited; ringsticking, piston scufiing and scratching and wearing away of other parts and material reduction of engine efliciency is thereby prevented.

Other additives have been developed which act as detergents in order to assist in the removal of soot, sludge, varnish, and/or lacquer formed from deterioration of the oil at high operating temperatures. Detergents, due to their cleansing action, prevent the build-up of these deleterious materials and assist in removing those formed. Anti-wear additives have the property of reducing friction of movable metal parts of the same or different metals. Due to the function exerted or property imparted by such additives on lubricants, wear caused by direct frictional contact of metals can be greatly reduced. Also additives have been developed for withstanding extreme pressures, dispersion of impurities, solubilizing of certain other additives, etc.

The large number of additives thus developed has been due to the fact that an additive is capable of functioning mainly in only one specific manner: very few lubricant additives have the ability of improving a lubricant in more than just one respect. Thus, a good anti-oxidant might not be able to inhibit lacqu'er and varnish formation on piston rods, or to act as a detergent or corrosion inhibitor. In many cases, it is found that whereas an additive possesses very good properties in one respect, this same additive is the cause of harmful deposits in another respect. A second and third additive is therefore frequcntly required in order to obtain a good stable lubricant. The combination of additives in lubricants wherein each additive exerts its influence without interfering with the function of other additives present is a difficult matter to attain because in most cases additives co-react or interfere with each other. occurring great care must be taken in selecting the additives, mixing them in specific proportions, and continuously watching and replacing additives which have stopped functioning or have deteriorated.

To prevent this from I to add to mineral lubricating oils, synthetic lubricants, and" the like, a multi functional material so as to inhibit oxidation and corrosion and prevent the formation of sludge, varnish and lacquer in said lubricants even under adverse operating conditions. Still another object of this invention is to use in lubricating compositions a material which prevents ringsticking as well as the sticking of other engine parts due to deterioration of the lubricant. Also it is an object of this'invention to use in lubricating compositions a material which inhibits wear, scuifing, scratching and other damage to engine parts. another object of this invention to provide novel compounds which possess multi-functional improving and enhancing properties when added to lubricants.

The above and other objects may be attained in accordance with the present invention by adding to oleaginous materials, e. g. various lubricating bases, a minor amount of a reaction product obtained by treating a saturated or unsaturated cyclic ketone fraction having at least 12 and preferably more than 18 carbon atoms in ,the molecule (which ketone fractions may be obtained from isophorone bottoms during its synthesis fIOm acetone by condensation as well as from other sources) with a phosphorus compound which is free from sulfur, and thereafter subjecting said phosphorized cyclic ketone to a sulfurization treatment at an elevated temperature. This reaction product may also be further treated with any, suitable metal such as alkali metals, alkaline earth metals, heavy metals, nitrogen containing organic bases and the like. Specifically, the above reaction product may be treated with such a compound as a hydroxide, carbonate or oxide'of Na, Li, K, Ca, Ba, Sr, Mg, Al, Zn, Cu, Cr, Cd, Fe, Mn, Ni, Sn, etc., or basic reagents such as ammonia, alkyl of aryl substituted ammonia, such as amines, quaternary ammonium compounds and the like.

The preferred ketones used to obtain the oil additive of this invention are the unsaturated cyclic ketones normally obtained from isophorone bottoms produced by condensation of acetone under elevated temperature and pressure. The isophorone bottoms thus produced may be fractionated into various cuts each of which may be used to form the reaction product of this invention. Among the specific isophorone fractions which may be used are topped crude isophorone bottoms, topped crude hydrolyzed isophorone bottoms, and the like.

The terms topped crude isophorone bottoms and topped crude hydrolyzed isophorone bottoms, and similar terms, which will be hereinafter used and fully described are generic and are used to identify various unsaturated cyclic ketone fractions of relatively high molecular weight obtained from acetone condensation. Unsaturated cyclic ketone fractions useable in reactions of the kind under consideration may be obtained by condensing acetone in 30% to 60% caustic so- It is still.

subjected to distillation to remove low boiling ketones having less than about 12 carbon atoms and other constituents and impurities. The product remaining in the still is purified by filtration, solvent treatment or the like, and comprises crude unsaturated cyclic ketones of high lution at a temperature ranging betweenmolecular weight, referred to herein as crude isophorone bottoms. The term isophorone bottoms as referred to herein is thus a complex mixture of high molecular weight unsaturated cyclic ketones containing at least 12 and preferably more than 18 carbon atoms in the molecule. The product formed is not to be confused with straight isophorone which is specifically 3,5,5-trimethyl cyclohexene-2-one-1, an unsaturated cyclic ketone containing only nine carbon atoms in the molecule. Isophorone bottoms produced by condensation of acetone under conditions referred to above included within itsscope any and all unsaturated cyclic ketones containing at least 12 and preferably more than 18 carbon atoms and having generally the chemical structural configcrude isophorone bottoms are topped crude isophorone bottoms which contain at least 15 carbon atoms in the molecule and which are obtained after removal of distillate from crude isophorone bottoms to a still head temperature of 284 F. at 10 mm. Hg pressure. Crude isophorone bottoms can be subected to hydrolysis with dilute sodium hydroxide, and the acetone and isophorone formed removed by distillation. The bottoms can then be filtered and purified and comprise essentially unsaturated cyclic ketones containing at least 12 carbon atoms in the molecule; these are referred to herein as crude hydrolyzed isophorone bottoms. This material can be subjected to distillation to split it into two fractions. The distilled hydrolyzed isophorone fraction has a boiling point of about 140 C. at 10 mm. Hg pressure and consists of a mixture of unsaturated cyclic ketones containing between 15 and 18 carbon atoms in the molecule. The residue is referred to as topped crude hydrolyzed isophorone bottoms, which is similar to topped crude isophorone bottoms. This residue comprises essentially unsaturated cyclic ketones of at least 15 carbon atoms in the molecule; Crude isophorone bottoms can be also subjected to condensation over solid sodium hydroxide to yield two types of resinous materials. The first resinous fraction or soft resin has a viscosity at 210 F. of about 25-26 centistokes and an average molecular weight of 320 to 350. The heavier fraction or medium resin has a viscosity at 210 F. of about to centistokes and an average molecular weight of 370 to 390. All of the various unsaturated cyclic ketone fractions obtained in the manner fully described above can be used for reacting with phosphorus sulfide to form a multi-functional lubricating additive. Other cyclic ketones having at least 12 carbon atoms are obtained by hydrogenating the above unsaturated cyclic ketones to obtain saturated cyclic ketones having at least 12 carbon atoms, alkyl cyclohexanone, i. e. dibutyl cyclohexanone, alkyl substituted carvomenthone, menthone, pulegone,

carvone, camphor, and the like having at least 12 carbon atoms.

The phosphorizlng agent which can be used to form the initial reaction product of this invention may be any sulfur-free phosphorus containing compound capable of reacting and introducing phosphorus into acyclic ketone. Specific phosphorizing agents may include elemental phosphorus, the phosphorus halides, oxyhalides, compounds of the oxygen family, e. g. P205, P203, etc.; metallic phosphides such as sodium or tin phosphides; phosphoric acid anhydride, said anhydride generally being accelerated by addition of acetyl chloride; phosphoric acid and the like.

The type of pho-sphorizing agent used, the ratio of the two reactants, the temperature, time and condition under which the reaction is to be carried out, as well as the manner in which the reaction product is recovered, may be varied within the limits described herein provided the phosphorus-chemically combines with the cyclic ketone of this invention. Phosphorization may be carried out in an inert solvent and/or under inert conditions, and depending upon the nature of the two reacting materials the temperature may vary between about 170 F. and about 350 F., although the range of 200F. to 250 F. is preferred.

The preferred phosphorizing agents are elemental phosphorus and phosphorus pentoxide, and the preferred ketone fractions which are reacted with said phosphorizing agents are topped crude isophorone bottoms which are residues remaining after removal of distillate from crude isophorone bottoms to a still head temperature of 284 F. at mm. Hg pressure, and comprising unsaturated cyclic ketones containing at least carbon atoms in the molecule. Another preferred fraction is a topped crude hydrolyzed isophorone bottoms obtained from crude hydrolyzed isophorone bottoms, similar to the topped crude isophorone bottoms. The term topped used throughout has the same meaning as in the petroleum art, namely, a distillation or fractionation step, whereby certain materials are removed as an overhead fraction.

The mol ratio of the phosphorizing agent to ketone may vary from about 1:2 to about 1:4, and even to about 1:8, of the phosphorizing agent to ketone depending upon the reactivity of the reactants. Also in carrying out the reaction it is advisable to initially control the reaction so that the temperature does not rise too rapidly. Generally it is preferred to keep the reaction at below 176 F. until all the reactants have been added and the reaction proceeds smoothly. Thereafter the temperature can be raised rapidly to the desired or optimum temperature.

Although not essential, the reaction should be carried out in a substantially inert atmosphere, and the two materials can be reacted per se or disposed in a suitable inert or non-reactive diluent and then reacted under conditions described above. This reaction product may be purified before subjecting it to the next reaction step or the crude product may be subjected to a sulfurization process which is the next step and thereafter recovered and purified.

The sulfurization of the phosphorized reaction product of the inventionis carried out at an elevated temperature and the sulfurizing agent may be selected from the class consisting of elemental sulfur, flowers of sulfur, sulfur halides,

- non-corrosive.

alkali polysiilflde, ammonium hydrogen sulfidehydrogen sulfide, sulfur dioxide and the like. Although the mol ratio of the sulfurizing agent such as sulfur and phosphorized cyclic ketone may be varied over wide limits, it is preferable to keep said reactants in a moi ratio of from about 0.5:1 to about 1:1.

The reaction should be carried out in substantially inert atmosphere .at a temperature of between about 250 F. and about 450 F., and preferably between 300 F. and 350 F. The sulfurization of the initial reaction product, namely a phosphorized ketone, may be carried cut progressively in the same-vessel, by simply adding the required amount of sulfur or the like and adjusting the reaction condition. Iithe initial reaction product has been purified first, it may be redispersed in a suitable diluent and then reacted with sulfur or the like in the manner described.

The exact mechanism of the sulfurization process is at present not understood. It appears however that the sulfur substantially replaces the phosphorus in the reaction product and becomes bonded in such a manner to the ketone as to be A great deal more sulfur enters into the reaction by this process than if cyclic ketone were simply sulfurized. It might be surmised that the sulfur causes the phosphorus to split out of the initial reaction resulting in an increase in the degree of unsaturation of the ketone thereby allowing more sulfur to react with the ketone. The final reaction product contains a major or substantial amount of chemically bond sulfur and a minor or minute amount of phosphorus which appears to be in the form of entrained material rather than as a chemically bond constituent of the final reaction product of this invention.

The final reaction product of this invention may be neutralized by treatment with-a suitable basic compound such as hydroxide, oxide or carbonate of an alkaline earth metal, alkali metal or other suitable basic reagent such as ammonia, alkyl or aryl amines, quaternary ammonium compounds or heavy metals such as Al, Cr, Fe, Sn and the like. Preferred reagents are Ca, Ba, Mg, Na, K, Al and Zn.

The entire reaction procedure of this invention is relatively simple and requires no elaborate or special equipment, undueprecaution or skill. The obtainment of the initial reaction product simply requires stirring an unsaturated cyclic ketone with phosphorus or phosphorus pentoxide, in an inert atmosphere, such as nitrogen or carbon dioxide. The temperature of the reaction should be increased gradually up to about F.

and maintained there until the reaction proceeds in an orderly manner. Thereafter it can be increased rapidly to above 300 Rand maintained there until the reaction is complete. The reaction product may be extracted with a non-aromatic solvent and the extracting medium removed by distillation or the like. The phosphorized ketone is then dispersed in a suitable solvent and a calculated amount of sulfur added under inert conditions and the mixture reacted for 2 to 8 hours at a temperature above about 250 F. to 300 F. or higher. The sludge like material formed during the reaction is removed and the product purified by solvent extraction, blowing and washing. If desired salts may be formed by agitating the reaction product in a suitable diluent such as mineral oil with a calculated amount of lime or any other desired neutralizing 7 agent at a temperature of above about 250 F. for about 2 hours. A stream of inert gas is usually blown through the mixture to remove any entrained moisture or other contaminates. The neutralized reaction product can be recovered from the oil by filtration and may be refiltered to remove excess lime, and other impurities.

To more clearly illustrate the present invention, the following examples are presented. It is to be understood, however, that various modifications can be resorted to without departing from the spirit of the invention as presented in the subjoined claims.

EXAMPLE I Part A A mixture of approximately, one mol of cyclic unsaturated ketones containing at least 18 carbon atoms in the molecule, obtained by topping bottoms from crude isophorone bottoms at a kettle temperature of between about 284 F. and mm. Hg pressure, and one mol of phosphorus pentoxide were stirred and heated in an inert atmosphere of carbon dioxide for about five hours at around 200 F. The mixture was initially maintained at about 140 F. and then heated to about 300 F. At the end of the reaction period, the reaction product was extracted with a non-aromatic hydrocarbon and the solvent removed by evaporation at steam temperature in a current of carbon dioxide.

Part B The above phosphorized reaction product was dispersed in a light hydrocarbon and reacted with sulfur for about 2 to 4 hours at between about 350 F. and 400 F. with constant stirring until the reaction was complete. The sludge formed during the reaction was removed and the sulfurized reaction product was recovered by extraction. It was soluble in mineral oil and contained a substantial amount of chemically bond sulfur and a minute amount of phosphorus.

EXAIVIPLEII A mixture of a ketone as used in Example I and phosphorus were reacted under the, conditions and isolated in the manner indicated in Example I (Part A). This phosphorized product was then reacted with sulfur for about four hours at between about 350 F. and 400 F. with constant stirring until the reaction was completed. The resultant product contained a substantial amount of sulfur and was readily soluble in mineral oil.

EXAMPLE III Approximately 10 parts of the reaction product of Example II was dissolved in a desired amount of mineral lubricating oil by gentle heating at about 190 F. to 212 F. To the mixture about parts of lime was added and a minor amount of water and the product heated for about two to three hours at about 212 F. The mixture was filtered to remove excess lime and the filtrate reheated for about two hours at between 250 and 270 F. A stream of nitrogen gas was blown through the mixture to remove entrained foreign matter, moisture and the like. This concentrate of Ca salt of the reaction product of this invention may be diluted with a desired mineral oil and used as an improved lubricant.

Reaction products of this invention are noncorrosive, possess the property of stabilizing lubricants against deterioration, and inhibit engine wear. I

Reaction products 01' this invention are excellent oil improving agents, imparting to oil fllm strength and extreme pressure properties as well as stabilizing said 011 against oxidation, corrosion, deterioration and the like.

Reaction products of this invention can be used as valuable additives to or constituents of heavy duty oils, motor oils, Diesel oils, aviation oils, synthetic oils, and the like, because of their anti-corrosion, anti-oxidation, and anti-wear properties. In addition, the reaction products of this invention may be used as stabilizing agents for other organic materials such as rubber, fuels, fatty oils, greases and the like. The amount of additive used can be varied over relatively wide limits but generally it is not necessary to use more than 5% by weight of the reaction product and preferably only between about 0.1% to 2.0% by weight is added to base lubricants.

The reaction product of this invention can be combined with other additives in lubricants, such as blooming agents, pour point depressants, viscosity improvers, extreme pressure agents, anti-foaming agents, and the like. Among the specific additives which can be used are oil-soluble detergents which include oil-soluble salts of various bases with detergent-forming acids. Such bases include metal as well as organic bases. Metallic bases includes the hydroxides, etc. of the alkali metals, Cu, Mg, Ca, Sr, Ba, Zn, Cd, A1, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases include various nitrogen bases as primary, secondary, tertiary and quaternary amines.

Examples of detergent forming acids are the various fatty acids of, say 10 to 30 carbon atoms, wool fat acids, paraffin wax acids (produced by oxidation of paraiiln wax), chlorinated fatty acids, rosin acids, aromatic carboxylic acids including aromatic fatty acids, aromatic hydroxy fatty acids, parafiln wax benzoic acids, various alkyl salicyclic acids, phthalic acid monoesters, aromatic keto acids, aromatic ether acids; diphenols as di(alkyl phenol) sulfides and di-sulfides, methylene bis alkyl phenols; sulfonic acids such as may be produced by treatment of' alkyl aryl hydrocarbons or high boiling petroleum oils with sulfuric acid; sulfuric acid mono-esters; phosphoric, arsenic and antimony acid mono and di-esters, including the corresponding thiophosphoric, arsenic and antimony acids; phosphonic and arsenic acids and the like.

Additional detergents are the alkaline earth phosphate di-esters, including the thiophosphate di-ester; the alkaline earth diphenolates, specifically the calcium and barium salts of diphenol mono and polysulfides.

Non-metallic detergents include compounds such as the phosphatides such as lecithin and cepholin, certain fatty oils as rapeseed oils, volatilized fatty or mineral oils and the like.

An excellent metallic detergentfor the present purpose is the calcium salt of oil-soluble petroleum sulfonic acids. This may be present advantageously in the amount of about 0.025% to 0.2% sulfate ash. Also alkaline metal salts of alkyl phenol-aldehyde condensation reaction products are excellent detergents.

Anti-oxidants comprise several types, for example, alkyl phenols such as 2,4,6-trimethyl phenol, pentamethyl phenol, 2,4-dimethyl-6-ter tiary butyl phenol, 2,4-dimethyl-6-octyl phenol, 2,6-ditertiary butyl-4-Inethyl phenol, 2,4,6-tritertiary butyl phenol and the like; amino phenols as benzyl amino phenols; amines such as dibutylphenylene diamine, diphenyl amine, phenyl-betanaphthyl amine, phenyl-alpha-naphthyl amine, dinaphthyl amine.

Corrosion inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 and more carbon atoms; alkali metal and alkaline earth salts of sulfonic acids and fatty acids; organic compounds containing an acidic radical in close proximity to a nitrile, nitro or nitroso group (e. g. alpha cyano stearic acid).

Extreme pressure agents which may be used comprise: esters of phosphorous acids such as triaryl, alkyl hydroxy aryl, or aralkyl phosphates, thiophosphates or phosphites and the like; neutral aromatic sulfur compounds of relatively high boiling temperatures such as diaryl sulfides, diaryl disulfides, alkyl aryl disulfides, e. g. diphenyl sulfide, diphenol sulfide, dicresol sulfide, dixylenol sulfide, methyl butyl diphenol sulfide, dibenzyl sulfide, corresponding diand trisulfides, and the like; sulfurized fatty oils or estersof fatty acids and monohydric alcohols, e. g. sperm oil, jojoba oil, etc., in which the sulfur is strongly bonded; sulfurized long chain olefins such as may be obtained by dehydrogenation or cracking of wax; sulfurized phosphorized fatty oils or acids, phosphorous acid esters having sulfurized organic radicals, such as esters of phosphoric or phosphorous acids with sulfurized hydroxy fatty acids; chlorinated hydrocarbons such as chlorinated paraffin, aromatic hydrocarbons, terpenes, mineral lubricating oil, etc., or chlorinated esters of fatty acids containing the chlorine in position other than alpha position.

Additional ingredients may comprise oil-soluble urea or thiourea derivative, e. g. urethanes, allophates, carbazides, carbazones, etc., polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high molecular weight oil-soluble compounds.

Depending upon the additive used and conditions under which it is used, the amount of additive used may vary from 0.01% to 2% or higher. However, substantial improvement is obtained by using amounts ranging from 0.1% to 0.5% in combination with phosphorus sulfide-unsaturated cyclic ketone reaction products of this invention.

It is to be understood that while the features of the invention have been described and illustrated in connection with certain specific examples, the invention, however, is not to be limited thereto or otherwise restricted, except by the prior art and the scope of the appended claims.

I claim as my invention:

' 1. A composition comprising a major amount of an oleaginous lubricating material and between about 0.1% and of a reaction product obtained by reacting at a temperature ranging from 170 F. to about 350 F., a sulfur-free phosphorizing agent with a high molecular weight unsaturated cyclic ketone fraction containing at least 12 carbon atoms in a ratio of from 1 :2 to 1:8, and thereafter treating the resulting reaction product with a suifurizing agent in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F.

2. A composition comprising a major amount of an oleaginous lubricating material and between about 0.1% and 5% of a reaction product obtained by reacting at a temperature'ranging from 170 F. to about 350 F., a sulfur-free phosphorizing agent with a high molecular weight unsaturated cyclic ketone fraction containing at least 12 carbon atoms and derived from condensation of acetone to higher molecular weight isophorone type products in a ratio of from 1:2 to 1:8, and thereafter treating the resulting reaction product with a sulfurizing agent in a ratio of from 0.521 to 1: at a temperature ranging from 240 to 450 F.

3. A composition comprising a major amount of an oleaginous lubricating material and between about 0.1% and 5% of a reaction product obtained by reacting at a temperature ranging from F. to about 350 F., a phosphorus oxide with a high molecular weight unsaturated cyclic ketone fraction containing at least 12 carbon atoms in a ratio of from 1:2 to 1:8, and thereafter treating .the resulting reaction product with sulfur in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F.

4. A composition comprising a major amount of a mineral oil and between about 0.1% and 5% of a reaction product obtained by reacting at a temperature ranging from 170 F. to about 350 F., a phosphorus oxide with a high molecular weigh unsaturated cyclic ketone fraction containing a least 12 carbon atoms in a ratio of from 1:2 to 1:8, and thereafter treating the resulting reaction product with sulfur in a ratio of from 0.5:1

to 1: at a temperature ranging from 240 to 5. A composition comprising a major amount of a mineral oil and between about 0.1% and 5% of a reaction product obtained by reacting at a temperature ranging from 170 F. to about 350 F., phosphorus pentoxide with a high molecular weight unsaturated cyclic ketone fraction containing at least 12 carbon atoms in a ratio of from 1:2 to 1:8, and thereafter treating the resulting reaction product with sulfur in the ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F.

6. A composition comprising a major amount of a mineral oil and between about 0.1% and 5% of a reaction product obtained by reacting at a temperature ranging from 170 F. to about 350 F., phosphorus pentoxide wlth a high molecular weight unsaturated cyclic ketone fraction containing at least 18 carbon atoms in a ratio 01 from 1:2 to 1:8, and thereafter treating the resulting reaction product with sulfur in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F.

7. A composition comprising a major amount of an oleaginous lubricating material and between about 0.1% and 5% of a metal salt of a reaction product obtained by reacting at a temperature ranging from 170 F. to about 350 F., a sulfurfree phosphorizing agent with a high molecular weight unsaturated cyclic ketone fraction containing at least 12 carbon atoms in a ratio of from 1:2 to 1:8 and thereafter treating the resulting reaction product with a sulfurizing agent in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F.

8. A composition comprising a major amount of a mineral oil and between about 0.1% and 5% of a metal salt of a reaction product obtained by reacting at a temperature ranging from 170 F. to about 350 F., phosphorus pentoxide with a high molecular weight unsaturated cyclic ketone fraction containing at least 18 carbon atoms in a ratio of from 1:2 to 1:8, and thereafter treating the resulting reaction product with sulfur in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F.

9. A composition comprising a major amount of a mineral oil and between about 0.1% and 5% of a calcium salt of a reaction product obtained by reacting at a temperature ranging from 170 F. to about 350 F., phosphorus pentoxide with a high molecular weight unsaturated cyclic ketone fraction containing at least 18 carbon atoms in a ratio of from 1:2 to 1:8, and thereafter treating the resulting reaction product with sulfur in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F.

10. A composition comprising a major amount of an oleaginous lubricating material and a minor amount sufiicient to stabilize said oleaginous material against deterioration and corrosion of a reaction product obtained by reacting at a temperature ranging from 170 F. to about 350 F., a sulfur-free phosphorizl'ng agent with a high molecular weight unsaturated cyclic ketone fraction containing at least 12 carbon atoms in a ratio of from 1:2 to 1:8, and thereafter treating the resulting reaction product with a sulfurizing agent in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F.

11. A process of producing a stable, non-corrosive reaction product comprising reacting at a temperature ranging from 170 F. to about 350 F. a sulfur-free phosphorizing agent with a high molecular weight unsaturated cyclic ketone fraction containing at least 12 carbon atoms, in a ratio of from 1:2 to 1:8, and thereafter treating th resulting reaction product with a sulfurizing agent in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to450 F.

12. A process of producing a stable, non-corrosive reaction product comprising reacting at a temperature ranging from 170 F. to about 350 F. a sulfur-free phosphorizing agent with a high molecular weight unsaturated cyclic ketone fraction containing at least 12 carbon atoms, in a ratio of from 1:2 to 1:8, and thereafter treating the resulting reaction product with a sulfurizing agent in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F., and finally neutralizing th product with a metal compound.

13. As a new composition, a sulfur-free phosphorus-containing unsaturated cyclic ketone fraction having at least 12 carbon atoms in the molecule obtained by reacting said unsaturated cyclic ketone fraction with a sulfur-free phosphorizing agent in a ratio of from 1:2 to 1:8, and thereafter treating the resulting reaction product with a sulfurizing agent in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F.

14. As a new composition, a metal salt of a sulfur-free phosphorus-containing unsaturated cyclic ketone fraction having at least 12 carbon atoms in the molecule obtained by reacting said unsaturated cyclic ketone fraction with a sulfurfree phosphorizing agent in a ratio of from 1:2 to 1:8, and thereafter treating the resulting reaction product with a sulfurizing agent in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F., and finally neutralizing the product with a metal compound.

15. As a new composition, a calcium salt of a sulfur-free phosphorus-containing unsaturated cyclic ketone fraction having at least 12 carbon atoms in the molecule obtained by reacting said unsaturated cyclic ketone fraction with a sulfurfree phosphorizing agent in a ratio of from 1:2 to 1:8, thereafter treating the resulting reaction product with a sulfurizing agent in a ratio of from 0.5:1 to 1:1, at a temperature ranging from 240 to 450 F., and finally neutralizing the product with a calcium compound.

DAVID E. ADELSON;

REFERENCES CITED The following references are of record in the Otto t al Jan. 11, 1949 

1. A COMPOSITION COMPRISING A MAJOR AMOUNT OF AN OLEAGINOUS LUBRICATING MATERIAL AND BETWEEN ABOUT 0.1% AND 5% OF A REACTION PRODUCT OBTAINED BY REACTING AT A TEMPERATURE RANGING FROM 170* F. TO ABOUT 350*F., A SULFUR-FREE PHOSPHORIZING AGENT WITH A HIGH MOLECULAR WEIGHT UNSATURATED CYCLIC KETONE FRACTION CONTAINING AT LEAST 12 CARBON ATOMS IN A RATIO OF FROM 1:2 TO 1:8, AND THEREAFTER TREATING THE RESULTING REACTION PRODUCT WITH A SULFURIZING AGENT IN A RATIO OF FROM 0.5:1 TO 1:1, AT A TEMPERATURE RANGING FROM 240* TO 450*F.
 7. A COMPOSITION COMPRISING A MAJOR AMOUNT OF AN OLEAGINOUS LUBRICATING MATERIAL AND BETWEEN ABOUT 0.1% AND 5% OF A METAL SALT OF A REACTION PRODUCT OBTAINED BY REACTING AT A TEMPERATURE RANGING FROM 170*F. TO ABOUT 350*F., A SULFURFREE PHOSPHORIZING AGENT WITH A HIGH MOLECULAR WEIGHT UNSATURATED CYCLIC KETONE FRACTION CONTAINING AT LEAST 12 CARBON ATOMS IN A RATIO OF FROM 1:2 TO 1:8 AND THEREAFTER TREATING THE RESULTING REACTION PRODUCT WITH A SULFURIZING AGENT IN A RATIO OF FROM 0.5:1 TO 1:1, AT A TEMPERATURE RANGING FROM 240* TO 450*F. 